US5349103A - Preparation of aromatic nitriles - Google Patents

Preparation of aromatic nitriles Download PDF

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Publication number
US5349103A
US5349103A US08/184,617 US18461794A US5349103A US 5349103 A US5349103 A US 5349103A US 18461794 A US18461794 A US 18461794A US 5349103 A US5349103 A US 5349103A
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United States
Prior art keywords
propionic acid
mol
water
mixture
reaction
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Expired - Lifetime
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US08/184,617
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English (en)
Inventor
Bilge Gulec
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BASF Corp
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Ciba Geigy Corp
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Assigned to CIBA-GEIGY CORPORATION reassignment CIBA-GEIGY CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GULEC, BILGE
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Assigned to CIBA SPECIALTY CHEMICALS CORPORATION reassignment CIBA SPECIALTY CHEMICALS CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CIBA-GEIGY CORPORATION
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/06—Preparation of carboxylic acid nitriles from N-formylated amino compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes

Definitions

  • the present invention relates to the preparation of aromatic nitriles by reacting corresponding aldehydes with hydroxylamine sulfate in propionic acid in the presence of a salt of propionic acid.
  • the invention relates to a process for the preparation of a nitrile of formula ##STR3## wherein R is hydrogen, C 1 -C 4 alkyl or phenyl, by reaction of an aldehyde of formula ##STR4## wherein R is as defined above, with hydroxylamine sulfate and subsequent dehydration, which process comprises carrying out the reaction in propionic acid in the presence of a salt of propionic acid by heating to an external temperature in the range from 140° to 165° C., preferably from 150° to 160° C., for 2 to 6 hours, preferably for 3 to 5 hours, under atmospheric pressure, and simultaneously distilling the mixture of propionic acid and water from the system until a solution forms, and thereafter removing the mixture of propionic acid and water at 100°-130° C., preferably 110°-120° C., by vacuum distillation, and then isolating the resultant nitrile by standard procedures.
  • R defined as C 1 -C 4 alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
  • An alkali metal salt preferably sodium propionate, may suitably be used as a salt of propionic acid.
  • R is preferably in 4-position and is preferably tert-butyl or, most preferably, phenyl.
  • the aldehydes of formula II are known compounds.
  • the propionic acid is conveniently used in an amount of 10 to 20 mol, preferably 15 to 18 mol, based on 1 mol of aldehyde.
  • Hydroxylamine sulfate is used in approximately stoichiometric proportion, preferably in slight excess, i.e. 0.505 to 0.58 mol, based on 1 mol of aldehyde.
  • Sodium propionate is suitably used in an amount of 1.05 to 1.3 mol, based on 1 mol of hydroxylamine sulfate.
  • nitriles obtained by the process of this invention am useful intermediates for, inter alia, the synthesis of diketopyrrolopyrrole pigments.
  • the external temperature is lowered to 120° C., a vacuum is applied, and a solvent mixture consisting of propionic acid and water is continuously distilled from the system over 2 hours at this temperature under a vacuum of c. 390 mbar.
  • the external temperature is then lowered to 120° C., a vacuum is applied, and a solvent mixture consisting of propionic acid and water is continuously distilled from the system over 2 hours at this temperature under a vacuum of c. 390 mbar.
  • the external temperature is then lowered to 120° C., a vacuum is applied, and a solvent mixture consisting of propionic acid and water is distilled from the system over 4 hours at this temperature under a vacuum of c. 400 mbar.
  • the external temperature is then lowered to 120° C., a vacuum is applied, and a solvent mixture consisting of propionic acid and water is continuously distilled from the system over 4 hours at this temperature under a vacuum of c. 400 mbar.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US08/184,617 1993-01-28 1994-01-21 Preparation of aromatic nitriles Expired - Lifetime US5349103A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH238/93 1993-01-28
CH23893 1993-01-28

Publications (1)

Publication Number Publication Date
US5349103A true US5349103A (en) 1994-09-20

Family

ID=4182440

Family Applications (1)

Application Number Title Priority Date Filing Date
US08/184,617 Expired - Lifetime US5349103A (en) 1993-01-28 1994-01-21 Preparation of aromatic nitriles

Country Status (7)

Country Link
US (1) US5349103A (ko)
EP (1) EP0609179B1 (ko)
JP (1) JP3756205B2 (ko)
KR (1) KR100352713B1 (ko)
CN (1) CN1038674C (ko)
DE (1) DE59400417D1 (ko)
TW (1) TW275617B (ko)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5502234A (en) * 1995-07-17 1996-03-26 Eastman Chemical Company Process for the preparation and separation of cyclopropanecarbonitrile
US5618965A (en) * 1995-03-09 1997-04-08 Ciba-Geigy Corporation Process for preparing aromatic nitriles
EP0790234A1 (de) * 1996-02-15 1997-08-20 Ciba Spezialitätenchemie Holding AG (Ciba Spécialités Chimiques Holding SA) (Ciba Specialty Chemicals Holding Inc.) Herstellung aromatischer Nitrile
EP1057807A1 (en) * 1999-06-02 2000-12-06 Kao Corporation Process for producing nitriles

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4441419A1 (de) * 1994-11-22 1996-05-23 Bayer Ag Herbizide Mittel auf Basis von 2,6-Dichlor-3-fluor-benzonitril und neue Zwischenprodukte
DE19518398A1 (de) * 1995-05-19 1996-11-21 Sueddeutsche Kalkstickstoff Verfahren zur Herstellung aromatischer Nitrile
WO1998005630A1 (en) * 1996-08-08 1998-02-12 Alliedsignal Inc. Process for the preparation of organic nitriles
US6222058B1 (en) * 1998-03-30 2001-04-24 Eastman Chemical Company Process for the manufacture of cyclopropanecarbonitrile
ITMI20012131A1 (it) * 2001-10-16 2003-04-16 Miteni Spa Procedimento per la preparazione di alo-benzonitrili
CN102391152B (zh) * 2011-09-28 2013-12-25 南京工业大学 一种对氟苯甲腈的合成方法
CN109748817B (zh) * 2019-01-22 2021-12-28 河北工业大学 一种由脂肪醛合成脂肪腈的方法
CN109748818B (zh) * 2019-01-22 2021-12-28 河北工业大学 一种对苯二甲醛肟化脱水合成对苯二甲腈的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4235807A (en) * 1979-07-02 1980-11-25 Thompson-Hayward Chemical Company Synthesis of 2,6-disubstituted benzonitriles
EP0080700A1 (en) * 1981-12-02 1983-06-08 Sumitomo Chemical Company, Limited A process for producing nitrile compounds
GB2198728A (en) * 1986-12-08 1988-06-22 Central Glass Co Ltd Preparation of trifluoromethylbenzonitrile from trifluoromethylbenzaldehyde
US5281744A (en) * 1992-03-02 1994-01-25 Shell Oil Company Process for the preparation of nitriles

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4235807A (en) * 1979-07-02 1980-11-25 Thompson-Hayward Chemical Company Synthesis of 2,6-disubstituted benzonitriles
EP0080700A1 (en) * 1981-12-02 1983-06-08 Sumitomo Chemical Company, Limited A process for producing nitrile compounds
US4456562A (en) * 1981-12-02 1984-06-26 Sumitomo Chemical Company, Limited Process for producing nitriles
GB2198728A (en) * 1986-12-08 1988-06-22 Central Glass Co Ltd Preparation of trifluoromethylbenzonitrile from trifluoromethylbenzaldehyde
US4808746A (en) * 1986-12-08 1989-02-28 Central Glass Company, Limited Preparation of trifluoromethylbenzonitrile from trifluoromethylbenzaldehyde
US5281744A (en) * 1992-03-02 1994-01-25 Shell Oil Company Process for the preparation of nitriles

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
C.A. 114:206700j (1991); Shi, et al. *
C.A. 85:93176e (1976); Liebecher. *
C.A. 90:15177m (1979); Olah, et al. *
Chemical Abstract 99:53294z (1983); Chiriac. *
Journal of Nanjing University, vol. 26(2) 1990, pp. 263 266. *
Journal of Nanjing University, vol. 26(2) 1990, pp. 263-266.
Y. Chem. Soc. 1933 IX p. 43; Shoppee. *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5618965A (en) * 1995-03-09 1997-04-08 Ciba-Geigy Corporation Process for preparing aromatic nitriles
US5502234A (en) * 1995-07-17 1996-03-26 Eastman Chemical Company Process for the preparation and separation of cyclopropanecarbonitrile
EP0790234A1 (de) * 1996-02-15 1997-08-20 Ciba Spezialitätenchemie Holding AG (Ciba Spécialités Chimiques Holding SA) (Ciba Specialty Chemicals Holding Inc.) Herstellung aromatischer Nitrile
US5763638A (en) * 1996-02-15 1998-06-09 Ciba Specialty Chemicals Corporation Preparation of aromatic nitriles
EP1057807A1 (en) * 1999-06-02 2000-12-06 Kao Corporation Process for producing nitriles
US6320067B1 (en) 1999-06-02 2001-11-20 Kao Corporation Process for producing nitrile

Also Published As

Publication number Publication date
KR940018357A (ko) 1994-08-16
JPH06271524A (ja) 1994-09-27
CN1038674C (zh) 1998-06-10
CN1099748A (zh) 1995-03-08
JP3756205B2 (ja) 2006-03-15
EP0609179A1 (de) 1994-08-03
EP0609179B1 (de) 1996-07-17
KR100352713B1 (ko) 2003-01-29
TW275617B (ko) 1996-05-11
DE59400417D1 (de) 1996-08-22

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